WO2001025362A1 - Feuille de transfert de photocatalyseur - Google Patents

Feuille de transfert de photocatalyseur Download PDF

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Publication number
WO2001025362A1
WO2001025362A1 PCT/JP2000/006825 JP0006825W WO0125362A1 WO 2001025362 A1 WO2001025362 A1 WO 2001025362A1 JP 0006825 W JP0006825 W JP 0006825W WO 0125362 A1 WO0125362 A1 WO 0125362A1
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WO
WIPO (PCT)
Prior art keywords
resin
sheet
layer
transfer film
photocatalyst
Prior art date
Application number
PCT/JP2000/006825
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English (en)
Japanese (ja)
Inventor
Nobuo Kimura
Akihiko Funamoto
Kazuo Ono
Original Assignee
Nippon Soda Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Soda Co., Ltd. filed Critical Nippon Soda Co., Ltd.
Priority to JP2001528521A priority Critical patent/JP4675535B2/ja
Publication of WO2001025362A1 publication Critical patent/WO2001025362A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane

Definitions

  • the present invention transfers a photocatalytic film with excellent long-term adhesiveness to any substrate such as plastic film, sheet, board, molded product, paper, wood, metal, etc., and provides antibacterial, deodorant, and harmful substances for photocatalyst.
  • Transfer sheet capable of imparting functions such as decomposition removal of soil, antifouling, antifogging, and droplets, a method for transferring a photocatalyst layer using the transfer sheet, and a photocatalyst layer obtained by the method.
  • molded products furthermore, there is no appearance defect such as transparent, film unevenness and non-uniform interference fringes on substrates of any shape such as plate, sheet and film of thermoplastic resin.
  • the film containing the photosemiconductor powder may contain an adhesive binder, and as the binder, a synthetic resin or an inorganic substance can be used.
  • the bonding layer can be formed on the surface of the article, on the coating containing the optical semiconductor powder, or on both, and can fix the coating containing the optical semiconductor powder on the surface of the article.
  • a synthetic resin, a silicone resin, and other inorganic substances JP-A-9-122771 discloses that a release layer is formed on a sheet substrate, a photocatalyst-containing layer is further formed thereon, and a corrosion-resistant intermediate layer is further formed thereon.
  • a transfer sheet which is formed and further has a pressure sensitive adhesive or a heat sensitive adhesive formed thereon. It is described that water glass, colloidal silica, polyorganosiloxane, fluoropolymer, acrylic silicone resin, zinc phosphate, cement, and the like can be suitably used for the corrosion resistant intermediate layer. Furthermore, there is described a method of transferring a photocatalyst layer by press-bonding or thermo-compressing a transfer target using the transfer sheet. Japanese Patent Application Laid-Open No.
  • 9-122473 discloses a transfer sheet in which a release material is applied to the surface of a sheet base material, and further overlaid, and a mixture of a photocatalyst and an adhesive is applied thereto, or a release material is applied to the surface of the sheet base material
  • a transfer sheet is described in which a material layer and an adhesive layer are sequentially superposed and applied, and a photocatalyst is embedded in the adhesive layer.
  • the adhesive include polyvinyl alcohol, starch, a mixture of atearliestmargin and water, rubber, vinyl chloride, and phenol resin. Further, there is described a method in which the transfer sheet is placed in a mold, and a resin member is injection-molded to transfer a photocatalyst to the surface of a molded product.
  • An adhesive has been proposed as one of the methods for easily fixing the photocatalyst on the substrate.However, since the strong photooxidation of the photocatalyst can easily oxidize and decompose organic substances, the photocatalyst can be used. It is difficult to use an organic resin as an adhesive for the purpose of transferring and adhering to a transfer object, and the main component of the photocatalyst layer was specifically composed of an inorganic substance having a weak adhesive force. Also, a method of transferring and bonding the photocatalyst layer via an adhesive layer has been proposed. In this case as well, when an organic material is used for the adhesive layer, the adhesive at the interface with the photocatalyst layer is used. As a result, there is a problem that the photocatalytic layer is decomposed, and the adhesive strength is reduced in a short time, and the photocatalytic layer is peeled off.
  • both the photocatalyst layer and the organic adhesive layer have poor adhesion, and there is a problem that they are peeled off during transfer and use.
  • an acrylic silicon resin can be used, but no specific example is described.
  • the method of producing a resin having a photocatalyst layer by transferring the photocatalyst layer is more advantageous than other methods in that the photocatalyst layer can be formed regardless of the shape of the substrate to be transferred.
  • the thickness of the photocatalyst layer is l ⁇ m or more, the wear resistance of the film decreases, such as cracking of the film. Therefore, it is preferable that the thickness be 1 or less.
  • the present invention is a transfer film or sheet provided with a photocatalyst layer on a base film or sheet.
  • the transfer film has no cracks or transfer leakage at the time of transfer, and the transferred film exhibits excellent long-term adhesion.
  • Adhesion consists of a photocatalyst layer, an inorganic layer, and an adhesive layer provided on a transfer film or sheet, film or sheet base material, which is a siloxane cross-linkable resin containing 60% by weight of silicone, in this order.
  • a photocatalyst layer, an inorganic layer, a resin having specific properties on a transfer film or sheet whose layer is a siloxane cross-linkable resin containing 0.5 to 60% by weight of silicone, or a film or sheet base material To solve the above problems by using a transfer film or sheet having layers provided in this order.
  • the resin is extruded onto a transfer film or sheet having a photocatalyst layer, and is coated and laminated, and the transfer film or sheet is pressed during the process of extruding the resin.
  • the present inventors have found that a photocatalyst layer having good properties and appearance and having excellent long-term adhesiveness can be industrially supported on a resin, thereby completing the present invention.
  • the adhesive layer has a silicone content of 0.5 to 60% by weight in terms of silicon dioxide.
  • a transfer film or sheet comprising a siloxane cross-linked resin containing
  • Consstitution 2 In a transfer film or sheet in which a photocatalyst layer, an inorganic layer, and an adhesive layer are provided in this order on the surface of a film or sheet substrate, the adhesive layer is 0.5 to 60% by weight in terms of silicon dioxide.
  • (Constitution 4) The transfer film or sheet according to any one of (Constitution 1) to (Constitution 3), wherein a primer layer is provided on the adhesive layer.
  • the primer layer is characterized by comprising a resin having a number average molecular weight of 20,000 or less and a glass transition point of 110 to 100 ° C. (Structure 4) or (Structure 5) Transfer film or sheet according to
  • R 1 represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group, or a chlorine atom)
  • R 2 represents an alkyl group having 1 to 8 carbon atoms.
  • n 4 is an integer of 2 to 4
  • 1 ⁇ + 112 + 113 + 114 Represents an integer of 4.
  • the resin portion of the siloxane cross-linkable resin of the adhesive layer is an acrylic resin, an epoxy resin, an acrylic silicon resin, or an epoxy silicon resin, wherein any of (Configuration 1) to (Configuration 9) is provided.
  • the inorganic layer is represented by the formula (II)
  • n represents an organoalkoxysilane or a hydrolyzed / condensed product of an alkoxysilane represented by the following formula: A transfer film or sheet according to any one of (Configuration 2) to (Configuration 12),
  • the photocatalyst layer is a photocatalyst particle composite containing 25 to 95% by weight of a metal oxide gel and / or a metal hydroxide gel.
  • the metal oxide gel and / or metal hydroxide gel in the photocatalyst layer is one or two selected from silicon, aluminum, titanium, zirconium, magnesium, diobium, tantalum, tungsten, and tin.
  • (Structure 16) The transfer film or sheet according to any one of (Structure 1) to (Structure 15), wherein the thickness of the photocatalyst layer is 1 or less.
  • (Structure 17) The transfer film or sheet according to any one of (Structure 2) to (Structure 16), wherein the total thickness of the inorganic layer and the photocatalyst layer is 1 m or less.
  • (Structure 19) A step of preparing the transfer film or sheet according to any one of (Structure 1) to (Structure 18), a step of pressing an adhesive layer surface of the transfer film or sheet against a surface of a transfer target, and A method for transferring a photocatalyst layer, comprising a step of peeling a substrate in a transfer film or a sheet,
  • the step of pressing the adhesive layer surface of the transfer film or sheet against the surface of the transfer object is a step of pressing the adhesive layer surface of the transfer film or sheet against the surface of the transfer object while applying heat.
  • (Structure 22) The method for transferring a photocatalyst layer according to any one of (Structure 19) to (Structure 21), wherein the shape of the transfer target is a plate, a sheet, or a film.
  • (Structure 23) A molded article provided with a photocatalytic layer obtained by the method according to any one of (Structure 19) to (Structure 22) is irradiated with light having an ultraviolet intensity of 3 mWZ cm 2 for 500 hours, and then subjected to JISK 5400 Of photocatalyst layer by grid tape method specified in Japan A molded article provided with a photocatalyst layer having an evaluation score of 6 or more;
  • (Constitution 24) A photocatalyst layer obtained by the method according to any one of (Constitution 19) to (Constitution 22)
  • a molded article provided with a photocatalyst layer characterized in that the total light transmittance of the photocatalyst layer and the adhesive layer or the total light transmittance of the photocatalyst layer, the inorganic layer and the adhesive layer to light having a wavelength of 550 nm is 70% or more. Molded products,
  • the transfer film or sheet having a photocatalyst layer is the transfer film or sheet according to any one of (Constitution 1) to (Constitution 18).
  • (Structure 26) A method for producing a resin structure having a photocatalyst layer according to any one of (Structure 26) to (Structure 27),
  • (Structure 29) The photocatalyst layer according to any one of (Structure 25) to (Structure 28), wherein the resin of the resin structure is a polycarbonate resin, an acrylic resin, a polyvinyl chloride resin, or a polystyrene resin. Resin manufacturing method,
  • (Structure 30) The resin structure having a photocatalyst layer according to any one of (Structure 25) to (Structure 29), wherein the resin of the resin structure has a plate shape, a sheet shape, or a film shape. Body manufacturing method,
  • the structure of the transfer film or sheet having a photocatalyst layer is a structure in which the structure of the photocatalyst layer 2 alone, the photocatalyst layer 2, and the adhesive layer 3 are laminated in this order on the surface of the substrate 1 on which the structure to be transferred is installed.
  • a structure in which layers 5 made of a resin having a number average molecular weight of not more than 200 and a glass transition point of 110 to 100 ° C. are laminated in this order can be exemplified.
  • a structure as shown in Figs. 1-3 is preferred ⁇ ,.
  • the film-like or sheet-like base material used in the present invention is not particularly limited, and can be appropriately selected from an organic material, an inorganic material, or a composite material thereof. Examples thereof include polypropylene, acrylic resin, polyethylene terephthalate, polyvinyl chloride, polycarbonate, and polystyrene.
  • the thickness of the substrate is preferably in the range of 3 m to 500 m, and more preferably in the range of 16 im to 100 m.
  • the surface of the substrate is preferably smooth, and a substrate having a thickness variation of 10% or less is particularly preferable for forming a photocatalytic layer having a uniform thickness.
  • any siloxane crosslinkable resin containing 0.5 to 60% by weight of silicone in terms of silicon dioxide can be used.
  • Acrylic resin, epoxy resin, polyester resin, urethane resin, alkyd resin, etc. can be used as the siloxane cross-linkable resin, but acrylic resin and epoxy resin have the best adhesion to the object to be transferred.
  • an acryl silicone resin or an epoxy silicone resin into which a crosslinkable alkoxysilane moiety or a halogenosilane moiety has been introduced can also be suitably used.
  • the proportion of the organic moiety in the silicone-containing siloxane crosslinkable resin is preferably at least 40% by weight.
  • the organic portion means a portion other than silicon equivalent in terms of silicon dioxide. If the amount is less than 40% by weight, the transfer to the transfer target will not be successful, and the long-term adhesiveness of the film will decrease.
  • a resin having a larger number of cross-linking points in the siloxane cross-linkable resin has better adhesion to the photocatalyst layer or the inorganic layer.
  • the crosslinking point is, for example, an ester or carboxylic acid in an acrylic resin, a hydroxyl group, an unsaturated bond, an alkoxy in an epoxy resin.
  • a silane portion and the like can be exemplified.
  • silicone When silicone is added as a cross-linking agent to the siloxane cross-linkable resin, the adhesion to the photocatalyst layer or the inorganic layer is improved.
  • the amount of addition is in the range of 0.5 to 60% by weight in terms of silicon dioxide, and the effect is most effective when it is in the range of 20 to 40% by weight.
  • the weight ratio indicates a combination of the two. If the amount of the silicone exceeds 60% by weight, the adhesiveness to the transfer object is deteriorated.
  • R represents an alkyl group having 1 to 8 carbon atoms (which may be substituted by an amino group, a carboxyl group, or a chlorine atom). Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, methoxymethyl, dimethylaminomethyl, methoxethyl, dimethylaminoethyl, Examples thereof include a chloroethyl group, a chloropropyl group, and an acetoethyl group.
  • R 2 represents an alkyl group having 1 to 8 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Examples thereof include a butyl group, a t-butyl group, a methoxymethyl group, a methoxethyl group, and an acetoethyl group.
  • Specific examples of the compound represented by the formula (I) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltriisopropoate.
  • methyltrichlorosilane methyltributanesilane, ethyltrichlorosilane, ethyltribromosilane, ⁇ -propyltrichlorosilane, ⁇ -propyltribromosilane, ⁇ -hexyltrichlorosilane, ⁇ —Hexyltribromosilane, ⁇ -decyltrichlorosilane, ⁇ -decyltribromosilane, ⁇ -decyltrimethoxysilane, ⁇ -decyltriethoxysilane, ⁇ -decyltriisopropoxysilane, ⁇ -decyltri-t-butoxysilane, n— N-octadecyltrichlorosilane, n-octadecyltrimethoxysilane, n-octadecyltrilane,
  • a light stabilizer and / or an ultraviolet absorber can be mixed in the adhesive layer for the purpose of improving durability.
  • a light stabilizer which can be used a hindered amine type is good, but other substances can also be used.
  • As the ultraviolet absorber a triazole type or the like can be used.
  • a silane coupling agent for the purpose of controlling the siloxane crosslinking reaction, a silane coupling agent, an acid-base catalyst, a metal chelate catalyst or the like can be added.
  • additives such as a surfactant and an antifoaming agent of 5% by weight or less can be added.
  • the thickness of the adhesive layer is 1 m or more, preferably 3 m or more. If it is less than l im, the transfer becomes difficult, and the long-term adhesion after the transfer deteriorates.
  • various printing methods such as gravure printing, roll coating method, flow coating method, sheet forming method, spray spraying method, dip coating method, spin coating method A method such as the law can be used.
  • the drying temperature varies depending on the material of the base sheet, the type of the solvent and the resin, but is generally preferably 150 ° C. or lower.
  • a mer layer is provided.
  • any material can be used as long as it is generally used, depending on the material of the transfer object.
  • resins having a number average molecular weight of more than 200,000 Alternatively, the number average molecular weight is not more than 20, 000, and the glass transition point is 110 to 100 ° C, preferably 10 to 80 ° C. C, and more preferably a resin in the range of 30 to 80 ° C. is used. In the case of a resin having a number average molecular weight of more than 200,000, its glass transition point is not restricted.
  • a resin having an elongation percentage of the coating film dried at room temperature to 60 ° C. in the range of 30 to 150%, particularly preferably in the range of 50 to 130%.
  • the material used for one layer of the polymer include a polyvinyl isobutyl ether, an acrylic ester resin, an olefin chloride resin, a rubber resin, a pressure-sensitive adhesive such as a polyethylene-vinyl acetate copolymer, or a styrene resin. Styrene-acrylic copolymer, acryl resin, phenol resin, epoxy resin, acryl silicone resin, epoxy silicone resin, urethane resin, polyester resin, etc., and acryl silicone resin or epoxy silicone resin is particularly preferable. .
  • the thickness of the primer layer is not particularly limited as long as it does not affect properties such as transparency, but is preferably in the range of 0.05 to 5 ⁇ m. At 0.05 m or less, there is no effect of improving adhesion, and at 5 ⁇ or more, the effect of improving adhesion does not change much.
  • the metal oxide gel and / or metal hydroxide gel in the photocatalyst layer not only fixes the photocatalyst and firmly adheres to the siloxane crosslinked resin of the adhesive layer, but also removes the photocatalyst layer from the base film or sheet after transfer. This has the effect of facilitating peeling. In addition, since the gel is porous, it has an adsorptive property and has an effect of enhancing photocatalytic activity.
  • the content of the metal oxide gel and / or metal hydroxide gel in the photocatalyst layer is preferably in the range of 25 to 95% by weight. If it is less than 25% by weight, the adhesion to the adhesive layer will be insufficient, and if it is more than 95% by weight, the photocatalytic activity will be insufficient.
  • the material of the metal oxide gel and metal or hydroxide gel include gay, aluminum, titanium, zirconium, magnesium, diobium, tantalum, tungsten, and tin. Also, these were mixed As the gel, a composite oxide gel prepared by a method such as a coprecipitation method can be used. In order to mix with the photocatalyst, it is preferable to mix in a sol state before forming a gel, or to mix in a raw material stage before preparing a sol. Gel preparation methods include hydrolysis of metal salts, neutralization decomposition, ion exchange, and hydrolysis of metal alkoxides. The photocatalyst powder is uniformly dispersed in the gel.
  • any method can be used as long as it can be obtained in the state described above.
  • a large amount of impurities are present in the gel, the adhesiveness and catalytic activity of the photocatalyst will be adversely affected. Therefore, a gel with few impurities is preferred. In particular, if the gel contains more than 5% of organic matter, the photocatalytic activity will decrease.
  • the photocatalyst of the photocatalyst layer T i 0 2, ZnO, S rT i 0 3, C d S, G aP, I nP, GaAs, B aT i 0 3, K2Nb0 3, F e 2 0 3, T a 2 0 5, WO 3.
  • SnO There B i 2 0 3, N i O, Cu 2 0, S i C, illustrate the S i 0 2, Mo S 2 , I nPb, Ru0 2, C e 0 2 , etc. And an anatase type titanium oxide is particularly preferable.
  • the following coating method can be used.
  • the photocatalyst can be dispersed in the state of a precursor solution of a metal oxide sol and a precursor of a metal or metal hydroxide sol, and can be hydrolyzed or neutralized during coating to form a sol or a gel.
  • an acid or alkali peptizer may be added for stabilization.
  • a surfactant, an antifoaming agent and a silane coupling agent can be added in an amount of 5% by weight or less based on the photocatalyst in the sol suspension.
  • the drying temperature at the time of forming the photocatalyst layer is preferably 50 ° C. or more and 150 ° C. or less, depending on the material of the base film or sheet.
  • the thickness of the photocatalyst layer is higher when the photocatalyst layer is thicker, but if it is 2 or more, the film may be cracked when the substrate sheet is peeled off after the completion of the transfer.
  • the value is 1 or less, a transparent film having a total light transmittance of 80% or more and a haze ratio of 2% or less of the film after transfer at a wavelength of 550 nm is obtained, and the appearance of the transfer object is not impaired at all. It is also useful in terms of sex.
  • the inorganic layer has the effect of improving the adhesion between the photocatalyst layer and the adhesive layer, the effect of improving the wear resistance of the photocatalyst layer, and the effect of reducing color development due to interference fringes derived from the photocatalyst layer thickness.
  • R represents an alkyl group which may have a substituent having 1 to 4 carbon atoms
  • R is an alkyl group which may have a substituent having 1 to 5 carbon atoms or 1 carbon atom.
  • n represents 0 or 1.
  • the main component is an organoalkoxysilane or a hydrolyzed / condensed product of an alkoxysilane represented by the following formula:
  • Specific examples of the silane compound represented by the formula ( ⁇ ) include those similar to the specific examples of the silane compound represented by the formula (I).
  • a silicic acid sol, an alumina sol, a zirconium sol, or the like can be added.
  • the same coating method as that for forming the adhesive layer can be used.
  • 5% by weight or less of a surfactant, an antifoaming agent and a silane coupling agent can be added.
  • the drying temperature at the time of forming the inorganic layer varies depending on the material of the base sheet, but is preferably from 50 ° C to 150 ° C.
  • the thickness of the inorganic layer is from 0.1 / m to 2 m, and preferably the total film thickness of the photocatalyst layer and the inorganic layer is from 0.1 ⁇ to 1 / m. If it is more than 2 m, the film may crack when the base sheet is peeled off after transfer is completed.
  • the transfer film or sheet of the present invention the photocatalyst layer, the inorganic layer, a resin having a number average molecular weight of 20,000 or more and / or a number average molecular weight of 20,000 or less, Further, a layer made of a resin having a glass transition point of 110 to 100 ° C. is provided in this order.
  • a resin having a glass transition point of 1 to 100 ° C, preferably 10 to 80 ° C (: more preferably 30 to 80 ° C) is used. Is preferred.
  • a resin having a number average molecular weight of 200,000 or more its glass transition point is not limited, and for example, a resin in the range of 110 to 100 ° C can be used. .
  • pressure-sensitive adhesives such as polyvinyl isobutyl ether, acrylic ester resin, chlorinated olefin resin, rubber resin, polyethylene-vinyl acetate copolymer, or styrene resin, styrene-acrylic copolymer, acrylic Examples thereof include a resin, a phenol resin, an epoxy resin, an acrylic silicone resin, an epoxy silicone resin, a polyurethane resin, and a polyester resin, and an acrylic silicone resin or an epoxy silicon resin is particularly preferred.
  • a light stabilizer and / or an ultraviolet absorber can be mixed in the resin layer for the purpose of improving durability.
  • a light stabilizer that can be used a hindered amine type is preferable, but other substances can also be used.
  • As the ultraviolet absorber a triazole type or the like can be used.
  • additives such as a surfactant and an antifoaming agent of 5% by weight or less can be added.
  • the thickness of the resin layer is at least ⁇ , preferably at least 3 m. If it is less than 1 m, transfer becomes difficult, and the long-term adhesion after transfer deteriorates.
  • the same coating method as when forming the adhesive layer can be used.
  • the drying temperature varies depending on the material of the base film or sheet, the type of the solvent and the resin, but is generally preferably 150 ° C. or lower.
  • a release layer can be provided on the base film or sheet for the purpose of making the base film or sheet easily peelable after the transfer.
  • the material melamine, silicon, fluorine, acrylic thermosetting resin alone or a mixture thereof can be used. It is also possible to adjust the peel strength by adding additives such as silicon, fluorine, polyester and polyethylene to the above resin.
  • Preparing the transfer film or sheet as a transfer method A method for transferring a photocatalytic layer, which includes a step of pressing the adhesive layer surface of the film or sheet against the surface of the transfer object and a step of peeling off the base material in the transfer film or sheet, can be exemplified.
  • the step of pressing against the transfer object can be performed by any method such as heating and / or pressing.
  • any method such as an in-mold transfer method for transferring at the time of production of a plastic molded article or a roll transfer method for transferring a film or a plate onto a plane can be used.
  • Methods for maintaining the cross-linking reaction point include reducing the hydrolysis rate of the cross-linking silicon alkoxy group (Si-OR) or replacing the cross-linking alkoxy group with an alkoxy group having a larger number of carbon atoms by an alkoxy exchange reaction. Or increasing the glass transition temperature of the resin part. Further, after the transfer film or the sheet substrate is peeled off, a post-treatment such as heating can be further performed. At this time, even if the crosslinking reaction is advanced in the adhesive layer, the adhesion is similarly improved.
  • a method in which the transfer film or sheet of the present invention is placed in a mold, a resin member is injection-molded, and a photocatalyst is transferred to the surface of a molded product can be exemplified.
  • the transfer target can be transferred in a complicated shape by using a method such as vacuum compression bonding.
  • a method such as vacuum compression bonding.
  • a plate, a sheet, or a film is particularly preferable.
  • the step of peeling the substrate in the transfer film or sheet is exemplified by a method in which the transfer sheet is peeled by applying shear stress, tensile stress, or the like, or a method in which the transfer sheet is peeled by using the oxidizing power of a photocatalyst by irradiating ultraviolet rays. be able to.
  • the sheet substrate After transfer, the sheet substrate also acts as a protective film to prevent damage to the photocatalyst layer unless it is peeled off.
  • the adhesiveness of the photocatalyst layer by the grid tape method specified in JISK540 was evaluated. It is a molded article provided with a photocatalyst layer having 6 or more points.
  • the molded article obtained by using the present invention comprises a photocatalyst layer and an adhesive layer or a photocatalyst layer.
  • the method for forming a photocatalyst layer on a resin according to the present invention is characterized in that a molten resin is extrusion-coated on a transfer film or a sheet having a photocatalyst and is continuously manufactured.
  • Extrusion coating can be exemplified by a method in which a molten resin is extruded into a film form from a slit die called a T-die and applied to a substrate.
  • a film having a three-layer structure including the photocatalyst layer, or a film having a four-layer structure including the photocatalyst and the adhesive layer can be continuously manufactured.
  • the adhesiveness can be further increased.
  • Another method of forming a photocatalyst layer on a resin according to the present invention is characterized in that a molten resin is extruded and laminated between a transfer film or a sheet having a photocatalyst and a substrate to be transferred, and is continuously manufactured.
  • Extrusion lamination in this case is also called sanguinche lamination, in which molten resin is extruded from a slit die into a film and applied to the substrate, and another substrate is supplied from an unwinder called a sanding machine Then, it shows the method of bonding together.
  • the transfer film or sheet can be used as a substrate coated with the molten resin or as a substrate supplied from the unwinder. In this case, a three-layer coated film or the like can be manufactured continuously.
  • Another method for forming the photocatalyst layer of the present invention on a resin is to press-bond a transfer film or sheet having a photocatalyst layer during the step of cooling the melt-extruded resin on a cooling port. It is characterized by being manufactured continuously.
  • This method is used in a method of mixing and heating materials and continuously extruding a molten resin from an extruder through a die, and in a chill roll method in which a resin is extruded and then rapidly cooled by a cooling roll.
  • a transfer film is laminated on the extruded resin and both are cooled at a time to produce a resin structure having a photocatalyst layer. Resin having photocatalyst layer
  • the material of the resin having the photocatalyst layer is not particularly limited as long as it is a thermoplastic resin, and specific examples thereof include a polyethylene resin, a polypropylene resin, and a polyethylene terephthalate resin.
  • a polyethylene resin a polypropylene resin
  • a polyethylene terephthalate resin a polyethylene terephthalate resin
  • acrylic resin, polyvinyl chloride resin, polycarbonate resin and polystyrene resin are particularly preferred.
  • the shape is not particularly limited, but is preferably a plate, sheet, or film.
  • the thickness is preferably in the range of 3 to 200 m, and more preferably in the range of 16 to 100 m.
  • the film surface should be smooth, but the surface may be uneven for the purpose of patterning during transfer.
  • the structure of a transfer film or sheet having a photocatalyst layer is a structure in which a photocatalyst layer alone, a photocatalyst layer, and an adhesive layer are laminated in this order on a substrate surface on which a structure to be transferred is placed, or a photocatalyst layer.
  • An example is a structure in which an inorganic layer, an inorganic layer, and an adhesive layer are laminated in this order.
  • a structure having an adhesive layer is preferable in consideration of the adhesion to the transfer target. Specific examples of the structure, material, and the like are preferably the transfer film or sheet described above.
  • 1 to 3 are diagrams schematically showing preferred structures in the transfer film of the present invention.
  • a photocatalyst coating liquid (Nippon Soda's Bidginga-1 NDC-1) is prepared by dispersing photocatalyst particles in silica sol on a polyethylene terephthalate film (Toyobo E5001) with a thickness of 2 ⁇ zm that has not been subjected to surface treatment. 30 C: solid content concentration 8%) After coating with a bar coater to a film thickness of 0.5 m, it was dried at 120 ° C to prepare a PET film with a photocatalytic layer (A-1).
  • a polysiloxane-added siloxane-crosslinked acryl resin solution Y (Nippon Soda's Vidova NRC-300A: solid content concentration 10%) is coated to a film thickness of 5 im, dried at 120 ° C, and transferred to a transfer sheet ( T-1) was created. Then, the acrylic resin plate surface as a transfer object, by superimposing the transfer sheet (T one 1), laminated with a 5 k pressure GZcm 2 at 180 ° C, peeling the substrate sheet, the outermost surface Prepared an acrylic resin plate (P-1) consisting of a photocatalyst layer.
  • (A-2) was produced under the same conditions as in Example 1 except that only the film thickness was 0.2 m. Furthermore, a polysiloxane-added siloxane crosslinked acryl resin solution (Nippon Soda's Vidova -NRC-300A: solid content concentration 10%) is coated to a film thickness of 5 m, dried at 120 ° C, and transferred to a transfer sheet. (T-2) was created. Then, the acrylic resin plate surface as a transferred object, overlapping the transfer sheet (T one 2), laminated with a 5 kg / cm 2 of pressure at 180 ° C, by peeling the substrate sheet, the outermost An acrylic resin plate (P-2) with a photocatalytic layer on the surface was prepared.
  • a polysiloxane-added siloxane crosslinked acryl resin solution (Nippon Soda's Vidova -NRC-300A: solid content concentration 10%) is coated to a film thickness of 5 m, dried at 120 ° C, and transferred to
  • (A-2) was prepared in the same manner as in Example 2, and (A-2) a coating solution of an inorganic layer (a glass power T 2106 solution and a glass power H 501 solution of Nippon Synthetic Rubber: 95: 5 was coated with a bar coater to a thickness of 0.3 and dried at 120 ° C to produce a PET film (B-1) with an inorganic layer of a photocatalyst layer. Furthermore, a polysiloxane-added siloxane cross-linked acrylic resin solution (Nippon Soda's Vistreta-NRC-300A: solid content concentration 10%) is coated to a film thickness of 5, dried at 120 ° C, and transferred to a transfer sheet (T- 3) was created.
  • a coating solution of an inorganic layer a glass power T 2106 solution and a glass power H 501 solution of Nippon Synthetic Rubber: 95: 5 was coated with a bar coater to a thickness of 0.3 and dried at 120 ° C to produce a PET film (
  • a transfer sheet (T-1) prepared in the same manner as in Example 1 was used as an acrylic resin film. (Kanebuchi Chemical Sanjuren 004NAT, thickness 50 m) and transferred at 140 ° C with a pressure of 5 kg / cm 2 using a heating and pressing roll. By peeling the transfer sheet substrate, an acrylic resin film (P-4) with the photocatalyst layer on the outermost surface was created.
  • the transfer sheet (T-3) prepared in the same manner as in Example 3 was overlaid on an acrylic resin film (Sanjuren 004NAT manufactured by Kaneka Chemical Co., thickness 50 / m) and heated at 140 ° C under a pressure of 5 kcm 2. Transfer was performed using a pressure roll. By peeling off the transfer sheet substrate, an acrylic resin film (P-5) having a photocatalyst layer on the outermost surface was created.
  • Example 1 transfer sheet was adjusted (T-1) a polystyrene resin plate (two Tsu Seo one resin, 2 mm thickness) overlaid, heat and pressure at 5 k gZcm 2 pressure at 80 ° C Transfer was performed using a roll. By peeling off the transfer sheet substrate, an acrylic resin film (P-6) with the outermost surface being a photocatalyst layer was prepared.
  • the transfer sheet (T-13) adjusted in the same manner as in Example 3 was placed on a polystyrene resin plate (made of Nippon Resin, 2 mm thick), and at 80 ° C. and a pressure of 5 kg / cm 2 . Transfer was performed using a heating and pressing roll. By peeling off the transfer sheet substrate, an acrylic resin film (P-7) having the photocatalyst layer on the outermost surface was created.
  • a transfer sheet (T-1) prepared in the same manner as in Example 1 a copolymer polyester solution Byron 300 (manufactured by Toyobo Co., Ltd.) was coated with a bar coater so as to have a film thickness of 0.5 ⁇ . After drying, the sheet was dried at 120 ° C to prepare a transfer sheet (T-4) with a single primer layer.
  • a transfer sheet (T-12) prepared in the same manner as in Example 2 an acrylic silicon resin solution ZEMRAC YC 3623 (manufactured by Kanegafuchi Chemical Co., Ltd.) was applied with a bar coater to a thickness of 0.5 m. After coating, it was dried at 120 ° C. to prepare a transfer sheet (T-5) with a primer layer.
  • the transfer sheet (T-5) is laminated on the surface of the polycarbonate plate, laminated at 150 ° C and a pressure of 5 kg / cm 2 , and the substrate sheet is peeled off. P-9) was created.
  • a transfer sheet (T-3) prepared in the same manner as in Example 3 an acrylic silicon resin solution Zemurac YC 3623 (manufactured by Kanegafuchi Chemical Co., Ltd.) was applied to the transfer sheet (0.5 mm) to a thickness of 0.5 m. After coating, the resultant was dried at 120 ° C. to prepare a transfer sheet (T-6) with a single primer layer.
  • a PET film with a photocatalytic layer and an inorganic layer in the same manner as in Example 3 except that Nissan Chemical Snowtex IPA-ST adjusted to 1% solid content with water Z ethanol 1 Z1 as the inorganic layer coating liquid was used.
  • B-2 transfer sheet (T-17), and resin plate (P-11) were adjusted.
  • a transfer sheet with a primer layer (T-10) and a resin plate (P-14) were prepared in the same manner except that a silicone resin solution ZEMRAC YC5920 (manufactured by Kaneka Chemical Co., Ltd.) was used.
  • Example 3 a PET film (B-1) with a photocatalyst layer and an inorganic layer was prepared. Further, the surface is coated with acryl silicone resin solution ZEMRAC YC 3623 (manufactured by Kane-buchi Chemical Co., Ltd.) using a bar coater so that the film thickness becomes 0.
  • acryl silicone resin solution ZEMRAC YC 3623 manufactured by Kane-buchi Chemical Co., Ltd.
  • the acrylic resin plate surface as a transfer object the transfer sheet (T - 1 1) a lap, laminated with a 5 k pressure GZC m 2 at 180 ° C, by peeling the base sheet, An acrylic resin plate (P-15) with a photocatalyst layer on the outermost surface was prepared.
  • the acrylic resin plate surface as a transferred object overlapping the transfer sheet (T one 12), and laminating over preparative at 5 kg / cm 2 of pressure at 180 ° C, by peeling the base sheet
  • an acrylic resin plate (P-16) with a photocatalyst layer on the outermost surface was prepared.
  • Comparative Example 2 L a siloxane cross-linkable resin, is coated with an acrylic resin-based transparent ink manufactured by Showa Ink Co., Ltd. as a coating liquid for the adhesive layer (A-1) to a thickness of 5 m on the film, and then dried at 60 ° C. Then, a transfer sheet (T-1 13) was created.
  • the above-mentioned transfer sheet (T-13) is laminated on the surface of the acrylic resin plate as the transfer object, laminated at 180 ° C under a pressure of 5 kg / cm 2 , and the base sheet is peeled off. Then, an acryl resin plate (P-17) having a photocatalyst layer on the outermost surface was prepared.
  • test plates (P-1) to (P-17) obtained in the examples were evaluated by the following methods.
  • the adhesiveness was evaluated by a cross-cut tape test specified in JIS K5400.
  • the interval between cuts was 2 mm, and the number of squares was 25.
  • the evaluation score was based on the criteria described in JIS K5400.
  • the adhesion was measured by a grid tape method specified in JISK 5400, and the durability was evaluated.
  • the evaluation score is the same as for the adhesiveness evaluation.
  • hydrophilicity measurement sample After washing the photocatalyst layer on the sample surface with ethanol, it was dried at 60 ° C for 30 minutes to obtain a hydrophilicity measurement sample. After irradiating the sample with light having an ultraviolet intensity of 2 mWZ cm 2 for 24 hours using black light, the contact angle of the surface with distilled water was measured with a contact angle measuring instrument (Elma 360 S type).
  • the evaluation criteria for hydrophilicity were as follows.
  • Comparative Example 1 since the metal oxide gel or metal hydroxide gel was not contained in the photocatalyst layer, the transfer was incomplete and the appearance was impaired, as well as the adhesiveness and durability. Only those with poor properties and poor photocatalytic activity were obtained.
  • Comparative Example 2 since a normal transfer resin was used for the adhesive layer, the resin was decomposed by the photooxidation action of the photocatalyst, and the film was peeled off in the durability test.
  • a photocatalyst core in which photocatalyst particles are dispersed in silica sol on a 25 / m-thick polyethylene terephthalate film (Toyobo E5001) with no surface treatment Apply a coating solution X (Nippon Soda's birisoner NDC-130 C: solids concentration 8%) with a mouth coater at a rate of 2 OmZ to a film thickness of 0.3 m at 120 ° C. After drying, a PET film with a photocatalyst layer (A-3) was prepared.
  • a polysiloxane-added siloxane-crosslinked acryl resin solution Y (Nippon Soda's bidover -NRC-300A: solid content concentration 10%) was coated at a rate of 2 OmZ using a roll coater to a film thickness of 3 ⁇ . After drying at 120 ° C, a transfer sheet (T_13) was prepared. Next, the molten polycarbonate is extruded from a die on a transfer sheet ( ⁇ -13), rapidly cooled by a cooling roll, and the base sheet is peeled off. P-18) was created.
  • the transfer sheet (T_13) prepared in Example 16 was laminated on a cooling roll, and the transfer sheet was subjected to the cooling step together with the polystyrene resin.
  • a polystyrene film (20-20) having the photocatalyst layer on the outermost surface was created.
  • test plates ( ⁇ -18) to ( ⁇ -20) obtained in Examples 16 to 18 were evaluated by the method described above, and the results are shown in Table 2.
  • Table 2 The characteristics of the test plates ( ⁇ -18) to ( ⁇ -20) obtained in Examples 16 to 18 were evaluated by the method described above, and the results are shown in Table 2.
  • the photocatalyst layer is firmly adhered to the object to be transferred by using the siloxane cross-linkable resin containing 0.5 to 60% by weight of silicon as silicon dioxide in the adhesive layer.
  • the strong photooxidation effect of the photocatalyst does not impair its adhesiveness, and in the long term, antibacterial, deodorant, release of harmful substances by photocatalyst, antifouling, antifogging, drip, etc. Function can be maintained. Further, a structure having a similar function can be obtained by transfer without using the above-mentioned adhesive layer and using a resin having specific properties.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne une couche mince ou une feuille de transfert d'un photocatalyseur comprenant une matière de base se présentant sous la forme d'une couche mince ou d'une feuille et, formée sur celle-ci dans l'ordre suivant, une couche adhésive ou une couche photocatalytique, une couche inorganique et une couche adhésive, caractérisée en ce que la couche adhésive comprend une résine réticulée par siloxane contenant 0,5 à 60 % en poids d'une silicone; une couche mince ou une feuille de transfert d'un photocatalyseur comprenant une matière de base se présentant sous la forme d'une couche mince ou d'une feuille et formées sur celle-ci dans l'ordre suivant, une couche photocatalytique, une couche inorganique et une couche de résine ayant des propriétés spécifiques; ainsi qu'un procédé de formation d'une couche photocatalytique sur un substrat consistant à extruder une résine sur la couche mince ou la feuille de transfert d'un photocatalyseur afin de donner un stratifié de revêtement, ou à presser la couche mince ou la feuille destinée au transfert d'un photocatalyseur sur une résine pendant le moulage par extrusion de la résine. La couche mince ou la feuille de transfert d'un photocatalyseur ne présente pas de craquelure ou d'omission de transfert et est excellente du point de vue de la durabilité de l'adhésivité de la couche mince après transfert; et le procédé formant une couche photocatalytique sur un substrat peut être utilisé comme procédé commercial de formation d'une couche photocatalytique présentant une bonne apparence et une bonne transparence, excellent du point de vue de la durabilité d'adhésivité sur n'importe quel substrat de façon uniforme.
PCT/JP2000/006825 1999-10-01 2000-10-02 Feuille de transfert de photocatalyseur WO2001025362A1 (fr)

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JP2005194309A (ja) * 2003-12-26 2005-07-21 Nippon Soda Co Ltd 接着層形成用組成物および光触媒担持構造体
JP2005296841A (ja) * 2004-04-13 2005-10-27 Fukuda Corporation:Kk 樹脂基材又は金属基材の加飾方法
JP2007326276A (ja) * 2006-06-07 2007-12-20 National Institute Of Advanced Industrial & Technology 機能性フィルムの製法及び製品
KR100892031B1 (ko) 2008-12-04 2009-04-07 김동현 접착 및 부착성이 매우 우수한 실리콘 전사시트
JP2010082965A (ja) * 2008-09-30 2010-04-15 Nissha Printing Co Ltd シート面の一部に金属薄膜を有し、アクリル系アンカー層を有する転写シート、及びその製造方法
JP2010099651A (ja) * 2008-09-25 2010-05-06 Panasonic Electric Works Co Ltd 複合材及びその製造方法
ITBO20120317A1 (it) * 2012-06-07 2013-12-08 Next Technology Tecnotessile Societ A Naz D Metodo di realizzazione di un pannello antibatterico.
WO2016139705A1 (fr) * 2015-03-02 2016-09-09 パナソニックＩｐマネジメント株式会社 Film de transfert et procédé de fabrication d'un film de transfert
WO2020116231A1 (fr) * 2018-12-04 2020-06-11 ハリマ化成株式会社 Feuille multicouche et matériau de transfert
WO2020116234A1 (fr) * 2018-12-04 2020-06-11 ハリマ化成株式会社 Résine moulée pourvue d'une couche de revêtement dur attachée et procédé pour sa production
CN111332056A (zh) * 2019-11-19 2020-06-26 江苏学泰印务有限公司 一种抗菌耐腐蚀热转印花膜及其生产工艺
WO2020203567A1 (fr) * 2019-03-29 2020-10-08 大日本印刷株式会社 Feuille de transfert
KR20200143714A (ko) 2018-04-12 2020-12-24 신에쓰 가가꾸 고교 가부시끼가이샤 광촉매 전사 필름 및 그의 제조 방법
KR20200143713A (ko) 2018-04-12 2020-12-24 신에쓰 가가꾸 고교 가부시끼가이샤 광촉매 전사 필름 및 그의 제조 방법

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Publication number Priority date Publication date Assignee Title
JP2005194309A (ja) * 2003-12-26 2005-07-21 Nippon Soda Co Ltd 接着層形成用組成物および光触媒担持構造体
JP2005296841A (ja) * 2004-04-13 2005-10-27 Fukuda Corporation:Kk 樹脂基材又は金属基材の加飾方法
JP4538720B2 (ja) * 2004-04-13 2010-09-08 株式会社フクダコーポレーション 樹脂基材又は金属基材の加飾方法
JP2007326276A (ja) * 2006-06-07 2007-12-20 National Institute Of Advanced Industrial & Technology 機能性フィルムの製法及び製品
JP4608682B2 (ja) * 2006-06-07 2011-01-12 独立行政法人産業技術総合研究所 機能性フィルムの製法及び製品
JP2010099651A (ja) * 2008-09-25 2010-05-06 Panasonic Electric Works Co Ltd 複合材及びその製造方法
JP2010082965A (ja) * 2008-09-30 2010-04-15 Nissha Printing Co Ltd シート面の一部に金属薄膜を有し、アクリル系アンカー層を有する転写シート、及びその製造方法
KR100892031B1 (ko) 2008-12-04 2009-04-07 김동현 접착 및 부착성이 매우 우수한 실리콘 전사시트
ITBO20120317A1 (it) * 2012-06-07 2013-12-08 Next Technology Tecnotessile Societ A Naz D Metodo di realizzazione di un pannello antibatterico.
JPWO2016139705A1 (ja) * 2015-03-02 2017-06-08 パナソニックＩｐマネジメント株式会社 転写フィルム及び転写フィルムの製造方法
WO2016139705A1 (fr) * 2015-03-02 2016-09-09 パナソニックＩｐマネジメント株式会社 Film de transfert et procédé de fabrication d'un film de transfert
US11319422B2 (en) 2018-04-12 2022-05-03 Shin-Etsu Chemical Co., Ltd. Photocatalyst transfer film and production method thereof
KR20200143714A (ko) 2018-04-12 2020-12-24 신에쓰 가가꾸 고교 가부시끼가이샤 광촉매 전사 필름 및 그의 제조 방법
KR20200143713A (ko) 2018-04-12 2020-12-24 신에쓰 가가꾸 고교 가부시끼가이샤 광촉매 전사 필름 및 그의 제조 방법
US11987682B2 (en) 2018-04-12 2024-05-21 Shin-Etsu Chemical Co., Ltd. Photocatalyst transfer film and production method thereof
WO2020116234A1 (fr) * 2018-12-04 2020-06-11 ハリマ化成株式会社 Résine moulée pourvue d'une couche de revêtement dur attachée et procédé pour sa production
JPWO2020116231A1 (ja) * 2018-12-04 2021-10-14 ハリマ化成株式会社 多層シートおよび転写材
JPWO2020116234A1 (ja) * 2018-12-04 2021-10-21 ハリマ化成株式会社 ハードコート層付モールド樹脂およびその製造方法
WO2020116231A1 (fr) * 2018-12-04 2020-06-11 ハリマ化成株式会社 Feuille multicouche et matériau de transfert
JP7345501B2 (ja) 2018-12-04 2023-09-15 ハリマ化成株式会社 多層シートおよび転写材
JP7434174B2 (ja) 2018-12-04 2024-02-20 ハリマ化成株式会社 ハードコート層付モールド樹脂およびその製造方法
WO2020203567A1 (fr) * 2019-03-29 2020-10-08 大日本印刷株式会社 Feuille de transfert
CN111332056A (zh) * 2019-11-19 2020-06-26 江苏学泰印务有限公司 一种抗菌耐腐蚀热转印花膜及其生产工艺

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